Authors:C. Păcurariu, R. Lazău, I. Lazău, R. Ianoş, and T. Vlase
The influence of the specific surface area on the crystallization processes of two silica gels with different specific surface
areas has been investigated in non-isothermal conditions using DTA technique. The activation energies of the crystallization
processes were calculated using four isoconversional methods: Ozawa-Flynn-Wall, Kissinger-Akahira-Sunose, Starink and Tang.
It has been established that, the decrease of the surface area from S=252.62 m2 g−1, in the case of sample GS2, to S=2.52 m2 g−1, in the case of sample GS1, has determined a slight increase of the activation energy of the crystallization process of the
gels. Regardless of the isoconversional method used, the activation energy (Eα) decreases monotonously with the crystallized fraction (α), which confirms the complex mechanism of gels crystallization.
It has been proved that the Johnson-Mehl-Avrami model cannot be applied for the crystallization processes of the studied silica
Authors:C. Ribeiro, W. de Souza, Marisa Crespi, J. Gomes Neto, and F. Fertonani
Tungsten carbide, WC, has shown dissimilar thermal behavior when it is heated on changeable heating rate and flow of oxidant
atmosphere. The oxidation of WC to WO3 tends to be in a single and slow kinetic step on slow heating rate and/or low flux of air. Kinetic parameters, on non-isothermal
condition, could be evaluated to the oxidation of WC to heating rate below 15°C min−1 or low flow of air (10 mL min−1). The reaction is governed by nucleation and growth at 5 to 10°C min−1 then the tendency is to be autocatalytic, JMA and SB, respectively.
Authors:M. Badea, R. Olar, E. Cristurean, D. Marinescu, M. Brezeanu, C. Calina-Soradi, and E. Segal
Data concerning the thermal behaviour of four heteropolynuclear compounds with the general formula [CuML(CH3COO)3] whereM=Ni(II), Zn(II), Mn(II) and Co(II); LH=2-amino-5-mercapto-1,2,3-thiadiazole were obtained. For the kinetically workable decomposition steps the values of the kinetic
parameters were estimated.
There are many reactions of interest in which one or more of the reactants belong to some solid phases. Modern thermoanalytical instruments can conveniently provide reaction kinetic data of high precision and accuracy, from which the underlying activation energyE may be derived in principle. Unfortunately, no ‘best' method yet exists for the derivation when the data have been collected with a programmed linear increase in sample temperature, unlike the case of isothermal measurements, which however suffer from experimental limitations . Here we propose a method for extractingE from non-isothermal data, that promises general validity.
A differential isoconversional non-linear procedure for evaluating activation energy from non-isothermal data is suggested.
This procedure was applied to model reactions (simulations) and to the dehydration of CaC2O4⋅H2O. The results were compared with those obtained by other isoconversional methods.
A new procedure for the prediction of the isothermal behaviour of the solid-gas system from non-isothermal data is suggested.
It bypasses the use of various approximations of the temperature integral that ground the integral methods of prediction.
The procedure was checked for: (1) simulated data corresponding to a first order reaction; (2) experimental data obtained
in the isothermal and non-isothermal decompositions of ammonium perchlorate. For the simulated data, a very good agreement
between calculated isotherms and those evaluated by means of the suggested procedure was obtained. A satisfactory agreement
(errors in time evaluation corresponding to a given degradation lower than 18%, for 0.10a0.37 and lower than 10% for 0.37a0.70)
was obtained for the experimental data corresponding to the decomposition of ammonium perchlorate. In this last case, the
mentioned differences between experimental and calculated data can be due both to the inherent errors in the evaluation of
the decomposition isotherms and to the dependence of the activation energy on the conversion degree.
A kinetic study of the crystallization of poly(ethylene oxide) (PEO) and of a blend of PEO+poly(bisphenol A-co-epichlorohydrin)
(PBE) was performed by using DSC in a non-isothermal program at constant cooling rates. The curves obtained were analyzed
by the Kissinger, Ozawa and Friedman methods, with determination of the kinetic parameters in each case. As a consequence
of the presence of PBE, the kinetic parameters were altered, leading to the conclusion that PBE has some influence on the
crystallization of PEO, modifying its mechanism.
Authors:M. Badea, R. Olar, E. Cristurean, D. Marinescu, A. Emandi, P. Budrugeac, and E. Segal
This paper deals with the investigation concerning the thermal stability of two new azo-derivatives and their Cu(II) complexes
of type [Cu(L1)2] and, respectively, ((C4H9)4N)2[Cu(L2)2]. The thermal decomposition steps have been put in evidence. For the kinetically workable ones, the values of the activation
energy vs. conversion degree were determined.
The topic of the present work is to study the thermal behavior of phenitoine and pharmaceuticals by means of kinetic parameters
determined in non-isothermal conditions.
The TG/DTG data were obtained at four heating rates. These data were processed by the following methods: Friedman (FR), Budrugeac-Segal
(BS) and the modified non-parametric kinetics (Sempere-Nomen).
The main conclusions of the kinetic study are
The FR method is versatile, but the values of the kinetic parameters are not certain, especially by multistep processes.
The BS method offer a non-variant part of the activation energy, but the kinetic description is only formal.
The NPK method is able to discriminate between two or more steps of a complex process. In our case, there are a preponderant
process (more than 70% of the explained variance).
By the NPK method there is a non-speculative separation of the temperature, respective conversion degree dependence of the
Summary The thermal behavior of KH2PO4, NaH2PO4 and Na2HPO4 under non-isothermal conditions using TG method with different heating rates was studied. The values of the reaction rate were processed by means of Friedman’s differential-isoconversional method. A dependence of the activation energy vs. conversion was observed. Therefore a procedure based on the compensation effect (suggested by Budrugeac and Segal) was applied. A less speculative data processing protocol was offered by the non-parametric kinetics method suggested by Serra, Nomen and Sempere. Three steps were observed by non-isothermal heating: a dehydration, a dimerization and a polycondensation. The differences in the intimate reaction mechanism are determined by the initial number of water molecules.